Diguanamines



Patented June 6, 1950 DIGUANAIWINES" JoIim-Kenson Si'mons; Toledo, Ghio, assignor to IiiBIW-O'wens-Fbnl' Glass Gompany; Toledo;

' Ohimacurpomfiomof Ohio No Drawing. Application September. I3, 1945.

Serial No. 6112152 4 Claims.

The invention. relatesi to novel carbon compounds that are diguanamines.

A guanamine is considered-to be a derivative of a carboxylic acid in which. the carboxy group is replaced by a fi-dian-rino-mtriazinyl radical. Hence a diguanamine;may be=considered to be a derivative of a dicarboxylic acid in which each of the two carboxy groups is replaced by a 4,6- diamino-2-triazi'nyl radi'cali digua-namines. heretoiore known-.- has: been obtainable only by methods that employexpen-.-

and advantages are apparent fromthehdescripw tion, which merely discloses and illustrates the invention? and is not intended to impose limitations upon the claims.

An application of thediguanaminesfif the-present invention that is, of considerable commercial importance is the use of such diguanamines in the same manner as melamine for reaction with formaldehyde to, produce. syntheticuresins.

The novel carbon compounds of. thelpresentr invention have the general formula NHa N-Hz wherein is. a pent'amethylene radical having the structural formula (a), (b) or (c), as follows:

CH2CH2C-GH2CH2 V The diguanamines of the present invention are uniquein that they may be produced readily and inexpensively by condensing with unsubstituted dicyandiamide the dinitrile corresponding to a dicarboxylic; acid havingithe generalv formula HOC$C*R'CCOI-I wherein R is the divalent 'radical hereinbefore described. The condensation of the dinitrile witl'n unsubstituted dicyand-iamide carried out by dissolvingastrongly-basic; catalyst in a suitable'primary. on secondary alcoholic solverrt such. as benzyli alcoho hoiiethylene glycol mono-methyk ether, adding the: dinitrileand; from. about 2.2- toabout 2.6 motes-on unsubstituted dicyandiamide: for each: mole of the: dini-tr-fle, andheating. to start the: reactions The: reactionis then con tinuedi by hsaiting: or coolingif necessary tokeep" the temperaturezbetweenabout 100 and about 180 6.. and toprevent-therreaction from becoming tocrviolent. 'I-he quantity -ofi-the alcoholic sol-= vent; used should be just'sufflcient to form assusyr pension. ot the: precipitate that can be stirred during the reactionr. When-precipitation of thediguanamine is complete, the precipitate is filtered off and washed with boiling water to remove excess dicyandiamide and product's of side reactions. The diguanaminermay be purifi-ed by converting it toa hydrochloride and neutralizing an aqueoussolution of the hydrochloride to liberate the diguanamine;

This method of pneparationiis versatile in that alargevariety. on dinitrilesmay, be used for the reactiomwith.dicyandiamide, to give a wide va'ri-. etyrotd'iguanamineslwhieh, by. reactionwith formaldehtydel produce...synthetic resins that have. widely varied-.Ipropertiesand therefore are suitable ion-various uses.

'Imeudinitrilesinwhieh.the.cyano groups are. separated by. five-carbon atoms. in series,.,ar1dwhichthe-central carbons-atom. of the series is disubstituted mayr be prepared by condensing; acnylonitrilerand a-.comp ound'.havingv an active methylene; group im the. presence... of a strong; base.

Example A solution of 288 grams of methyl ethyl ketone in 600 grams of tertiary butyl alcohol containing 20 grams or? a 30 per cent methanol solution of potassium Hy roxide is -ke'pt ata; temperature between .0 and 5 C. and stirred for five hours during; the-dropl-by-drop. addition ofv 320 grams of acrylo'ni'tril. An oil? layer that separates soon solidifies. After two more hours of stirring at 5 C.. the solid product is filtered off and air dried to produce an 88 per cent yield of gammamethyl-gamma-acetyl pimelonitrile. After 33.5 grams of this product and 33.5 grams of dicyandiamide have been added to 75 grams of benzyl alcohol in which has been dissolved two grams of 85 per cent potassium hydroxide, the mixture is warmed. By the time the temperature reaches 130 C., heating is no longer necessary and exothermic reaction continues spontaneously for to minutes. The ingredients are then kept at 140 to 160 C. by heating for two hours longer. Then after the mixture has been cooled the solid is filtered off and washed with alcohol to produce a crude product, which may be purified by boiling it with water and filtering it off from the hot water. The purified product is a 65 per cent yield of a substance that is insoluble in water and soluble in a dilute acid and may be crystallized from benzyl alcohol, which is gammamethyl-gamma-acetyl pimeloguanamine NH: NH:

N N CH: N N

A procedure is carried out that is the same as the procedure of Example 1, except that the initial ingredients are 98 grams of mesityl oxide, 100 grams of tertiary butyl alcohol, five grams of a 30 per cent aqueous solution of trimethylbenzylammonium hydroxide, and 106 gramsof acrylonitrile; the intermediate product is 66 grams of gamma isopropenyl gamma acetyl pimelonitrile; and the final ingredients are 51 grams of the intermediate product, 42 grams of dicyandiamide, fiVe grams of 85 per cent'potassium hydroxide and 100 grams of benzyl alcohol. The final product is 45 grams of a substance that melts at 2'73-4 C., which is gamma-isopropenylgamma-acetyl pimeloguanamine.

A procedure is carried out that is the same as the procedure of Example 1 except that the initial ingredients are 166 grams of fiuorene, 500 grams of dioxane, five grams of a 30 per cent aqueous solution of trimethylbenzyl-ammonium hydroxide, and 111 grams of acrylonitrile; the intermediate product is 60 grams of bis-cyanoethyl fluorene; and the final ingredients are 13.6 grams of the intermediate product, 8.4 grams of dicyandiamide, one gram of potassium hydroxide and 20 grams of benzyl alcohol. The final product is a 62 per cent yield of bis-(4,6-diamino2 triazinyl-ethyl) fiuorene.

Various other compounds embodying the invention may be prepared to meet various requirements.

Having described the invention, I claim:

1. A novel carbon compound having the general formula:

wherein R- is a pentamethylene radical of the class consisting of (a), (b) and (0), having the following structural formulas:

3. A novel carbon compound having the struc- 4. A novel carbon compound having the structural formula JOHN KENSON SIMONS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. A NOVEL CARBON COMPOUND HAVING THE GENERAL FORMULA: 